吡啶酮结构分散染料的合成及其偶氮-腙式异色机理

Synthesis and azo-Hydrazone Heterochromia Mechanism of Disperse Dyes Containing Pyridone Groups

研究了(N-乙基-3-氰基-4-甲基-5(-4-硝基偶氮苯)-6-羟基-2-吡啶酮)(D1)和(N-乙基-3-氰基-4-甲基-5-(2-氯4-硝基偶氮苯)-6-羟基-2-吡啶酮)(D2)这2种吡啶酮分散染料在溶剂(DMF和CH_(2)Cl_(2))和织物(涤纶和锦纶)上的偶氮-腙式异构行为,分析染料在极性和非极性溶剂中的吸收光谱差异,染料在涤纶和锦纶织物上的异色行为。运用高斯计算模拟染料的优化构型以及在溶剂和无溶剂状态下的染料吸收光谱,研究吡啶酮染料在不同环境下的偶氮-腙式存在形式。核磁共振氢谱(1 H NMR)表明,吡啶酮结构分散染料在极性溶剂中以偶氮结构存在,在非极性溶剂中以腙式结构存在。染色结果结合量子计算表明,染料在涤纶织物以腙式结构存在,在锦纶织物以偶氮结构存在。此外,吡啶酮分散染料在涤纶织物表现出超高的耐光色牢度,而在锦纶织物上的耐光色牢度较差,染料在异种织物上耐光色牢度的巨大差异归因于染料在不同织物上呈现出不同的分子结构。

(E)-1-ethyl-6-hydroxy-4-methyl-5-((4-nitrophenyl)diazenyl)-2-oxo-1,2-dihydropyridine-3-carbonitrile and(E)-5-((2,4-dinitrophenyl)diazenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile,namely D1 and D2 were synthesized,color performance in solvents,DMF and CH_(2)Cl_(2),as well as polyester and polyaimde fabrics are studied to investigate azo-hydrazone tautomerism behaviors of disperse dyes containing pyridone group.The visible absorption spectrophotometry behaviors in solvents are studied,and the heterochromic dyeing performance on polyethylene terephthalate(PET)and polyamide(PA)fabrics is also compared.To reveal azo-hydrazone tautomerism of pyridone disperse dyes induced by circumstances,Gaussian simulation is applied to give optimized geometries,as well as absorption spectrum in solvent and non-solvent environment.Nuclear magnetic resonance(1 H NMR)spectrum shows that the disperse dyes with pyridinone structure exist as azo form in polar solvents and hydrazone tautomer in non-polar solvents.The dyeing performance and quantum calculation show that the dyes exist in hydrazone form on PET fabric and azo structure in PA fabric.Pyridone disperse dyes show excellent light fastness on PET fabrics,but poor light fastness on PA fabrics,which is attributed to azo-hydrazone tautomerism of the dyes.